TWI305668B - Composition and method for copper chemical mechanical planarization using polysulfide slurries - Google Patents

Description

。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 This invention relates to an improved slurry composition and a method of chemical mechanical polishing or planarization of a semiconductor wafer. More specifically, it relates to a slurry composition containing a sulfur-containing compound capable of converting copper into copper sulfide, which is used to illuminate a stone wafer for manufacturing a semiconductor wafer. [Prior Art] In the fabrication of integrated circuits, semiconductor wafers for semiconductor fabrication generally perform a number of process steps, including deposition, patterning, and etching steps. Details of these semiconductor wafer fabrication steps are reported in The Annais 0f the International Institution for Production Engineering

Research (39/2/1990), Tonshoff et al., "Abrasive Machining of Silicon", pages 621-635. In each fabrication step, it is often necessary or desirable to modify or refine the exposed surface of the wafer to prepare a wafer for subsequent fabrication or fabrication steps. In the Baizhi semiconductor manufacturing system, the Shixi wafer receives a number of processing steps, which deposit a uniform layer of two or more discontinuous materials to form a single layer that becomes a multilayer structure. In this process, 'any method commonly used in the art is used to apply a uniform layer of the first material to the wafer itself or to an existing intermediate structural layer, in which holes are etched or traversed, and then filled with a second material. This pocket. Alternatively, the approximately uniform thickness characteristic of the first material can be deposited (usually

〇:\89\8%46 DOC 1305668 This layer is completed on the wafer, or on the pre-fabricated layer of the wafer, and then filled with the second material to accept this feature. After the deposition step, the deposited material or layer on the surface of the wafer typically requires further processing prior to additional deposition or subsequent processing. When finished, the surface is substantially flat and flat on the surface of the wafer. A designated example of this process is metal inlaying. In the damascene process, the pattern is etched into an oxide dielectric (eg, SiCh). After etching, an adhesion and/or barrier layer is deposited on the oxide surface. Typical barrier layers can include groups, nitrided groups, nitrided or chin, or tungsten. Second, a metal (eg, copper) is deposited over the adhesion and/or barrier layer. The copper metal layer is then modified, warp, or trimmed by removing copper metal and adhesion and/or barrier layer regions on the surface of the underlying dielectric. In general, removing enough surface metal causes the exposed surface outside the wafer to contain metal and oxide "electrical materials. The top view of the exposed wafer surface shows the flat surface of the copper metal with the corresponding etched pattern and the dielectric material of the adjacent copper metal. Copper (or other metal) and oxide dielectric materials on the modified surface of the wafer inherently have different hardness values and are subject to controlled corrosion. The method of modifying the surface of the semiconductor can be a combination of physical and chemical processes. This process is called chemical mechanical planarization (CMP). The abrasive CMP method used to modify the metallization process must be designed to modify both the metal (e.g., copper) and the dielectric material without scraping off the surface of the material. This grinding method must be! A flat outer exposed surface is fabricated on a wafer having exposed metal regions and exposed dielectric material regions. Chemical mechanical polishing (or planarization) (CMP) is a region that undergoes rapid changes in semiconductor processing. CMP provides overall (mm size) on the wafer surface

〇; \89\89646 DOC 1305668 and local (micron to nanometer size) flattening. - This + can improve the wafer coverage of dielectric materials and metals (eg, copper), and increase the freedom of lithography, etching, and deposition processes. Each equipment company has improved CMP technology by improving the CMP engineering scene, while chemical companies focus on gargles such as slurry and polishing pads. For example 'modifying or refining structured wafers

The conventional CMP method for the surface of the round road is a technique for polishing the surface of a wafer by using a slurry containing a plurality of slack abrasive particles. In general, the slurry is applied to the polishing pad' and then the wafer surface is ground or relatively moved to remove the desired material from the wafer surface. The slurry typically also contains a chemical that reacts with the surface of the wafer. An alternative to the CMP slurry method, which uses a grinding ruthenium, flattens the surface of the semiconductor, thereby eliminating the need for the above-described slurry containing polishing particles. This alternative CMP method is reported in International Notice No. 97/11484, published on March 27, 1997. The polishing pad has a textured abrasive surface comprising abrasive particles dispersed in a binder. In polishing, often in the presence of a working slurry containing no additional abrasive particles, the action of modifying the single layer of material on the surface of the wafer causes the polishing pad to contact the surface of the semiconductor wafer, thus providing a flat, uniform wafer surface. A working slurry is applied to the surface of the wafer under the action of the abrasive article to chemically modify or facilitate removal of material from the wafer surface. The prior art abrasive slurry used in the above process (in combination with the above-mentioned slurry or polishing pad) is generally a variety of additives (including a binder, an oxidizing agent, a purifying agent, a surfactant, a wetting agent, a buffering agent, a viscosity modifier, or these additives). A combination of) aqueous slurry. Additives can also be included with the wafer surface

第二 \89\89646 The second material on D〇C 1305668 (for example, a metal or metal alloy conductor) is a reactive agent such as an oxidation, reduction, passivation, or a miscible agent. An example of such a work-grinding can be found in, for example, U.S. Patent Application Serial No. 09/091,932, filed on June 24, 1998. Variables that can affect wafer CMP processing include the choice of proper contact pressure between the wafer surface and the abrasive article, the type of slurry medium, the relative velocity and relative motion between the wafer surface and the abrasive article, and the flow rate of the slurry medium. These variables are related and are chosen based on the individual wafer surfaces being processed. Because of the sub-micron-sized metal features found on the wafer surface, the CMP method of modifying the deposited metal layer until the barrier layer or oxide dielectric material is exposed to the outer surface of the wafer is only marginal. The removal rate of the deposited metal should be relatively fast to minimize the need for additional expensive CMP tools and the metal must be completely removed from the unnamed area. The metal remaining in the etched area must be limited to discontinuous areas where continuity is maintained to ensure proper conductivity. In other words, the metal modification method must be uniform 'controlled' and re-reformable for the submicron to nano scale. In the above CMP method, 'concave twist grinding performance, scratches or defects, and metal removal rate are (10) performance measurements. These performance measurements can be based on the usage of the job grinding. The concave twist grinding is a measure of how much metal (such as copper) is removed from the wire under the surface of the bonded or intermediate crystal. For example, after removing the concealed copper or copper plus barrier layer, the copper and the barrier or the upper layer of the dielectric layer are high. The difference is defined. Removal rate (4) The amount of material removed per unit time. = The removal rate of the clock is greater than at least about 丨 Å. The lower the removal rate, the less the better, such as hundreds of angstroms per minute (Angstroms per minute) or less, as it tends to follow the wafer.

O:\89\89646.DOC 1305668 Manufacturing generates an increase in total manufacturing costs (owner costs). In order to minimize the distortion of the concave distortion and increase the removal rate of the layered surface material on the semiconductor device, it is important to design a narrow concentration range and a fissure crack. The pH of the abrasive for polishing the semiconductor device depends on the composition of the surface layer to be polished. In most cases, it is desirable to design a grind with a suitable pH to effectively produce an oxide layered surface at the same rate as mechanical polishing to remove the layered oxide. For copper polishing and grinding equipment, U.S. Patent No. 783 shows the importance of forming copper oxide (1) about 6 ◦ yang. Cuprous oxide can be formed in near-neutral to microscopic media. In the low pH slurry, no protective oxide is formed on the copper surface, thus increasing the tendency of the oxidizing agent to aggressively attack the copper metal. In high pH milling, the removed copper can be precipitated by the solution, causing unwanted particulate matter to adhere to the wafer surface. Therefore, the copper polishing slurry must be formulated in a narrow pH window to determine the high yield after CMP. The pioneering skills of CMP include the following: US Patent 4,233,1 12 (Dart Industries), in which Valayil and

Eiias discloses the use of polysulfide as a catalyst for argon peroxide, which can be used to accelerate the dissolution of copper from a circuit board in the future. This early disclosure can be presumed to remove copper from wafers, which is the basis of many pioneering techniques. Acceleration of the removal rate of sulfur compounds has become a major focus of many patent documents. In the WO 0144396 patent (R〇del Holding), Sachen et al. describe a slurry containing mercaptans, disulfides and glycolates which demonstrates accelerated copper removal rates. In the WO 0Π2740 patent (Cabot Micr〇electr〇nics), Wang et al. also describe the organic sulfur sulphide 89\89646 DOC -10- 1305668 as a removal rate enhancer. In the WO OU 2741 patent (Cabot), Wang et al. re-described the organic sulfur corrosion accelerator which also contains a corrosion "stopping agent" in the composition. U.S. Patent No. 6,1,795 (1^11^§丨(:), where?" (: 11 discusses the use of organosulfur compounds as corrosion inhibitors for metal removal compositions. In U.S. Patent No. 6,068,879, Pasch reveals The use of similar compounds in post-etch cleaners. U.S. Patent No. 5,073,577 (Morton International),

Anderson discusses a high molecular weight polysulfide stabilizer that cures to form a sealant. In McNeU, Jones, and Little's Production of Sulfide Minerals by Sulfate-Reducing Bacteria During Microbiologically Influenced Corr〇si〇n 〇fc〇pper, it was proved that under certain conditions, chalcopyrite (cws) was formed on the copper surface. Non-adhesive layer. A p〇urbaix diagram has also been published which details the conditions for copper sulfide and oxide stabilization. . Accordingly, it would be desirable to provide an improvement in chemical mechanical planarization by providing an operational polishing m that can be used to modify the exposed intermediate copper surface of a structured wafer for semiconductor fabrication, and to provide for modifying the exposed copper intermediate surface of the semiconductor fabrication wafer. Preferably, the method has an improved, continuous copper removal rate, and an operation of the above types. Specially expected to provide a working slurry that is more stable than commercially available grinding. It is also desirable to provide an operation of the copper-containing structured wafer which can be used in the above method and which is preferably flat and less defective. [Invention] The present invention is useful for modifying the structure of a semiconductor manufacturing structure. The surface is worn and fatigued.

〇'>89\R%46. DOC-11 - 1305668 Method for exposing the interfacial surface of a structured wafer, and a semiconductor wafer fabricated according to the above method. However, for the present invention, the slurry is It may or may not contain abrasive polishing particles or any other solid that does not completely dissolve. Further, the term "grinding slurry" may refer only to sulfur-containing compounds which convert copper into copper sulfide. The present invention is a modified slurry composition and a semiconductor wafer t chemical mechanical polishing or planarization method for grinding a composition containing a sulfur compound capable of converting copper into copper sulfide, which is used for modifying or refining a suitable semiconductor The intermediate surface of the structured wafer used in fabrication. In one aspect, the present invention provides a working slurry that can be used to modify a copper surface suitable for wafers used in the fabrication of semiconductor devices, the slurry comprising the following: a) a sulfur-containing compound that converts copper to copper sulfide, b) Liquid carrier to be used as appropriate, c) oxidizing agent to be used as appropriate, d) inorganic polishing particles to be used as appropriate, e) tongs used as appropriate, f) buffers as appropriate, g) used as appropriate Passivating agent, h) surfactants, emulsifiers, viscosity regulators, wetting agents, lubricants, soaps, etc., as appropriate, i) use metal polishing selective stopping compounds as appropriate, j) use as appropriate Co-solvent. Another embodiment of the present invention is a method of modifying a wafer surface suitable for use in the fabrication of a semiconductor device, comprising the steps of: 0\S9\S9646.DOC -12- 1305668 a) providing a wafer, a package thereof,匕S has a material for etching the pattern, and a second material deposited on the surface of the first surface of the first surface of the first material; the third material can be converted into copper sulfide, and the operation of the B L1 mouthpiece is ground. 'Sub-down' causes the second material of the round to contact the abrasive; and c) relatively moves the wafer or polishing pad, the same, #吏 The first material is in contact with the polished 1 inch round exposed surface is flat and covered B Guangzhao 3 at least one exposed first-material area and one exposed second material area. The invention also includes the manufacture of a metal surface comprising the slurry of the invention. [Embodiment] x is used to remove copper and "golden" compositions from the surface (such as for wafer manufacturers). The use of the composition in a chemical mechanical planarization method for fabricating a semiconductor wafer. The CMP polishing (four) of the present invention is an important part of a sulfur-containing compound containing copper to convert copper sulfide, and is theoretically limited. It is believed that the sulfur-containing compound that converts copper to copper sulfide can adjust the copper removal rate to the desired range to effectively promote the copper sulfide (1) or copper („) layer, which in turn is abraded from the surface of the electronic device. In addition, the sulfur-containing compound of the present invention which converts copper to copper sulfide is characterized by the manufacture of an insoluble copper sulfide complex which minimizes the tendency of copper to deposit on the back side of the crucible device. The composition of the present invention contains a sulfur-containing compound which converts steel into copper sulfide, and an aqueous, organic or mixed aqueous-organic liquid carrier, optionally used oxidizing agent, optionally used inorganic polishing particles, depending on the case, Clamping agent for use, buffer as appropriate, passivation as appropriate 0 \80\89646 DOC -13 - 1305668 agent, surfactant used as appropriate, viscosity modifier as appropriate, used as appropriate Wetting agent, lubricant used as appropriate, soap used as appropriate. As discussed above, the inventive solution containing a sulfur-containing compound that converts copper to copper sulfide effectively removes copper and copper alloy layers, barrier layers, and dielectrics found in electronic devices in various CMP abrasive slurries. effective. In particular, the slurry of the present invention containing a sulfur-containing compound capable of converting copper to copper sulfide can be used to remove copper on an integrated circuit (as in a damascene structure, a sulfur compound which can be converted into copper sulfide by a manufacturer) This is accomplished within the scope of the invention by the delivery of sulfur to the surface of the copper and the vehicle of any material. Some preferred embodiments of the invention, but by no means limiting, are mono- and dithiocarbamate 'sulphuric acid, There are ash and ashless dithiophosphates and various other sulfur-containing materials, inorganic sulfides, organic sulfides, and organometallic sulfides. The term "sulfide" includes tellurides which can be mono-, di- or polysulfide. Preferably, the CMP slurry of the present invention typically comprises at least one soluble or partially soluble disulfide or polysulfide. A plurality of disulfides or poly: can be: wherein 1 and 112 are independently organic or Inorganic functional group. The organic moiety may include a hydrocarbon or a functional group such as hydrogen, an amine, a auxiliaries, a base, a thiol group, a fluorenyl group, or a class thereof. The base may include an alkali or an alkaline earth metal. Salt or ammonium salt or its group "Level, the average exit junction χ above, may be from zero to 247 = polysulfide. ♦ main sulfur with ethyl

O:\89\89646 DOC •14· I3〇5668 Surrounded* Name:. By hitting six iJ-degrees, the sulfur compound which converts copper into copper sulfide is concentrated in effectively maintaining the concentration of active sulfide required to promote copper sulfide: the concentration of the copper sink is removed. Preferably, the sulfur-containing compound composition which converts copper into sulfur steel has from about 1% to about (10)%, more preferably from about 5% to about 75% 'and still more preferably about} In addition to the concentration of sulfur to copper sulfide, the cMp slurry can contain an oxidizing agent to promote copper removal. ★ For fruit use, suitable chemical oxidants include chlorine peroxide, copper chloride; ammonium, sodium and potassium persulfate; ferric chloride; potassium ferricyanide; tartaric acid, potassium nitrate, pin acid, and potassium 'Amine, diethyl (tetra)amine, round offense, money metal complex (such as occupational compound, EDTA ammonium iron, citric acid iron, iron citrate, ammonium oxalate), and combinations thereof. The concentration of the oxide in the ionic water may range from about 〇 〇丨 to 〇 重量%, preferably from 0. G2 to 4G; e. /" Where hydrogen peroxide is used as the oxidant, the basin is generally from about 1% to about 15%, preferably from about 5% to about 5%, and most preferably from about 1 to about 5%. 5. The concentration in the range of % is present in the aqueous solution. The CMP slurry may also contain additives such as polishing particles, primary and secondary buffers, chelating agents, passivating agents, surfactants, emulsifiers, viscosity modifiers, Wetting agents, lubricants, soaps, organic or inorganic co-solvents, etc. The polishing particles for L may be inorganic or organic abrasive particles. These abrasive particles may be used to increase the removal rate of copper metal and/or dielectric. Examples include K Al2〇3, Ce〇2, oxidization, carbon, selenium, stone, stone, and titanium dioxide. The average particle size of these inorganic particles

〇 '89\8%46 DOC -15- 1305668 and more preferably less than about 1,000 angstroms, preferably less than about 500 angstroms, about 250 angstroms. . Preferably, the working abrasive comprises less than 1% by weight, preferably less than 2% by weight, and more preferably less than 5% by weight of inorganic particles. While the abrasive particles can be added to the CMP abrasive, the three-dimensional abrasive particles used in the (10) process can be fixed to the abrasive polishing art and preferably provide a substantially abrasive-free abrasive coating. In addition, the crystal of the present invention may not involve polishing particles in the abrasive incinerator of the present invention or on the polishing pad. The abrasive device of the present invention may also contain a buffer. Buffers can be added to work with polysulfide grinding to help with pH control. As noted above, pH can have a significant effect on the nature of the copper surface and the rate of copper removal. The optimum buffer is compatible with semiconductors, post-CMP cleaning requirements, and reduced potential impurities (such as alkali metals). In addition, the optimal buffer is adjusted to cover the pH range from acid to near neutral to alkaline. When the proton is completely or partially deprotonated with a base such as ammonium hydroxide, the mono-, di-, and polyprotonic acids may be used as a buffering agent. The ammonium salt of the acid is preferred, but other carboxylic acid bases and alkaline earth metal salts may be used. Representative examples include salts of carboxylic acids (e.g., monocarboxylic acids, dicarboxylic acids, dicarboxylic acids, with polycarboxylic acids). Preferred compounds include, for example, malonic acid, oxalic acid, citric acid, tartaric acid, succinic acid, hydroxysuccinic acid, adipic acid, salts thereof, and mixtures thereof. The nitrogen-containing compounds that can be buffered by the slurry include: aspartic acid, glutamic acid, histidine, lysine, glutamic acid, ornithine, cysteine 'tyramine, and carnosine, strontium ( 2-hydroxyethyl)imido-based (hydroxymethyl) A, ginseng (sulfhydryl) amine-based oxime, N-(2-ethylamino)_2-iminodiacetic acid, 1,3 -贰[参(hydroxydecyl)decylamine]propane, triethanolamine, ginseng(hydroxyindole) O:\89\89646DOC -16 - 1305668 acid, 1,3-hydrazine [paras(methyl)methylamine] Propane, triethanolamine, N-gin (methyl)methylglycine, N,N-indole (2-hydroxyethyl)glycine, and glycine. Ammonium hydrogen hydride can also be used in the grinding and burning of the present invention. The pH may range from about 2 to about 13, preferably from about 3 to about 1, and most preferably from about 4 to about 1. The slurry of the present invention may also comprise a copper chelating agent. Copper removal from the wafer surface can be enhanced by using a miscible or clamping agent in the CMP slurry of the present invention. Oxidation and dissociation of copper is enhanced by the addition of a binder which combines copper to increase the solubility of dissolved copper metal or copper oxide in an organic or aqueous medium. In the working slurry of the present invention, the complexing agent is always present at a concentration of from about 1 to about 5 weight percent. In the flattening of copper, the preferred intercalating agent is the following acid or salt: # 酸酸, iminodiacetic acid, phosphonic acid 2-aminoacetic acid, amine mono(methylenephosphonic acid) Isoethyldiphosphonic acid, diethylenetriamine penta (methylene phosphonic acid), and glycine. The concentration of the clamping agent may range from 0.001 / 〇 to about 50 / 〇 weight ratio 较佳 preferably from about 5% to about 1 〇〇 / 〇 by weight, and preferably from 1% to about 1% by weight. ratio. The abrasive rupture of the present invention may also comprise a passivating agent (i.e., a 'injective inhibitor). Copper corrosion inhibitors or passivating agents are known. It is known that copper is slightly purified by cuprous oxide, especially at neutral or mild pH. Adding a purifying agent to the working abrasive to protect the surface area of the steel that has not been in contact with the abrasive particles is not premature, is excessively removed by the oxidizing agent or controlling the concentration of the oxidizing agent that reacts with the exposed metal surface. The copper inhibitor is the most widely known and widely used copper inhibitor. Tolyl III. Sitting, gas thiobenzoyl σ 塞 u sitting, ugly ugly - Luo derivative). 4 open two saliva, and its materials (known as.

O:\89\89646 DOC 1305668 ^, surface finish, and flatness). The preferred concentration (weight percentage) of the working abrasive is from about G.G25% to about Q.2Q%, preferably from about Q Q to about 0.15. /. And more preferably in the range of about 〇5〇% to about 〇1〇%. The t-grinding slurry of the present invention T also comprises a viscosity tarant to obtain a desired viscosity of from about 5 centipoise to about 25 centipoise. Examples of viscosity modifiers include "PolyoxTM from η Carbide and BF~. Heart-~ρ〇〇1ΤΜ. Those skilled in the art should have 帛, as required for specific applications, surfactants, viscosity modifiers and Other known additives may be added to the working slurry. The slurry of the present invention may also comprise a suspending compound having the ability to inhibit system polishing in at least a portion of one or more layers of the multilayer substrate. Suitable for stopping the adsorption of the compound to the multilayer substrate. a first metal layer, a second metal layer, and/or one or more additional layers, and at least partially inhibiting layer removal of the slurry of the present invention. Preferably, the suspending compound at least partially inhibits the second of the slurry Layer removal. The term "at least partially inhibited" as used herein means that the system has at least about 10:1, preferably at least about 3:1, more preferably at least about %", and most preferably at least about 100: The first layer of 1: the second layer of polishing selectivity. The suspending compound can be any suitable cationic π-electric nitrogen-containing compound selected from the group consisting of amines, imines, decylamines, quinones, polymers thereof, and mixtures thereof. Suitable suspending compounds also include, for example, cationic charged nitrogen-containing compounds selected from the group consisting of amines, imines, guanamines, quinones, polymers thereof, and mixtures thereof, wherein the suspending compound is not included A sulfur compound or a pyrrole compound. Cationic charging as used herein means that the compound is deprotonated by a portion (e.g., > 1 〇/〇) at the operating pH of the system of the present invention. Preferably, the stop compound is also reversed by the surface charge of the unpolished metal layer

0 \89\89646 DOC -18- 1305668 Strip. The mill t of the present invention may contain various cosolvents to aid in the dissolution of sulfur compounds which convert steel into cupped copper. Depending on the copper sulfide, it can be converted to copper sulfide, and the solvent can be completely water or completely organic. In the dry circumference of the present invention, a mixed organic solvent of water and a suitable organic solvent may be used, including methanol, ethanol, and ri. "Tongtian. Knowing Isopropyl, Tetrahydrofuran, Dimethyl yam, Acetonitrile, Dimethyl Formamide, N-methylpyrrolidin-2-one. The slurry of the present invention may contain various emulsifiers. The slurry of the present invention may be used in a range of from about 7 to about TC (more preferably from about hunger to about 6 〇). C' and preferably from about 20. 〇 to about 5 (TC. The method of the present invention for modifying a wafer surface suitable for semiconductor device fabrication comprises the steps of: a. providing a wafer having a surface having an etched pattern a material, and a second material deposited on the surface of the first material; b. the second material of the round contact is combined with the polishing 塾 used in the invention. The abrasive 包含 contains a plurality of loose abrasive particles dispersed in the grinding And c. relatively moving the wafer while causing the polishing and (iv) germanium to contact the exposed surface of the wafer until the wafer is flat and includes at least one exposed first material region and one exposed second material region. This method is preferably about modifying the structure The intermediate surface of the circle. This first material is referred to as an intermediate material or an adhesive/barrier layer to which the dielectric material 7 is applied. Some suitable intermediate materials or adhesion barrier layers include buttons, titanium, nitrided groups, and titanium rat. Other suitable intermediate materials or adhesion/barrier layers include gold

0.\89\89646 DOC , 19-1305668 genus, nitride, and telluride. The design incorporating the first material includes a smear-like region, a recessed region, a via, and other components that make up the complete semiconductor device. Structure. The second material is typically a conductive material selected from the group consisting of titanium, silver, aluminum, tungsten, copper, or alloys thereof. The method is particularly suitable for modifying conductive surfaces of materials having a resistivity value generally less than about 0.1 ohm-cm. Generally, preferred dielectric materials have a dielectric constant of less than about 5. In this grievance, a working slurry containing a sulfur compound which converts copper into copper sulfide, and optionally inorganic particles, is as described above. The movement between the round and the polishing pad occurs in a range generally ranging from about 〇·丨 to about 25 psi, preferably from about 〇·2 to about 15 psi, and most preferably from about 1 to about 0 psi. . The wafer and polishing pad can be rotated and/or moved relative to each other in a circular manner, in a spiral manner, in an uneven manner, such as in a figure-eight elliptical manner, or in a random movement manner. The wafer holder or susceptor can also oscillate or vibrate, such as by transmitting ultrasonic waves through the holder or susceptor. For example, the polishing pad or wafer or polishing pad and wafer are rotated relative to one another and move linearly along the wafer and the opposite center of the pad. The rotational motion or rotational speed between the polishing pad and the wafer can be from 1 paw to (7) ... (eight) rpm. The preferred speed of the pad is from 1 rpm to 1,000 rpm, and more preferably from 1 〇卬 111 to 25 〇卬, and most preferably from 10 rpm to 60 rpm. The preferred speed of the wafer is 2 卬 111 to 1, 〇〇〇 rpm, more preferably 5 rpm to 5 rpm, and still more preferably 1 至 to 1 (8) rpm. The C Μ P slurry of the present invention can be used without mixing inorganic polishing particles in an aqueous medium. In addition, the use of a plurality of abrasive particles extending through at least a portion of the thickness of the fixed or fixed three-dimensional polishing pad allows for the removal of some particles during planarization of 0\89\89646 DOC -20- 1305668 to expose other preferred abrasive polishing defects. Contains multiple particles. Abrasive particles with a flattening function. Abrasives fixed and dispersed in the adhesive t-grinding and polishing method 'fixed grinding and only contact and movement between wafers until the exposed wafer surface is flat, and in the first - or the conductive material area And at least the brother of the road or the dielectric material area. - - 枓 (4) u is removed by one or more intermediate materials or barriers I. After removing excess conductive material, the exposed surface of the electrical material is usually essentially free of intermediate materials. Or == expose the surface of the intermediate material. The wafer can be continuously modified and then the wafer: the surface dielectric material and the metal layer β can be used for the grinding of the abrasive wafer of the present invention. The shape can be circular, for example, in the form of a grinding disc. The outer edge of the circular grinding disc is preferably smooth or may be fan shaped. The abrasive article can also be in the form of an ellipse or any polygonal shape such as a triangle, a square, a rectangle, or the like. Alternatively, the "grinding" can be in the form of a belt or in the form of a belt, which is commonly referred to as a belt roller in the (10) polishing industry. The belt roller can be indexed while the process is modified. The abrasive article can be perforated to provide an opening σ through the abrasive coating and/or liner to allow the abrasive (tetra) f to pass before, simultaneously or after use. The interfacial pressure (i.e., contact pressure) between the abrasive particles and the wafer surface is typically less than about 30 pounds (psi), preferably less than about 15 psi, and more preferably less than about 6 PSi. Two or more processing conditions can also be used in the flattening process. For example, the first processing segment can include a higher interface pressure than the second processing segment. During the flattening process, the rotation and switching speed of the wafer and/or the polishing pad can also be

O:\89\8Q646 DOC 21 l3〇5668 Change. The recessed portion of the polishing pad acts as a passage to distribute the working slurry over the entire circumference of the dome. The recessed portion can also serve as a passage for the grinding of the sulphide particles to aid in the removal of wear and other debris from the interface between the wafer and the abrasive article. The recessed portion also prevents the phenomenon of "stagnation" known in the art where the abrasive article tends to adhere or be inserted into the wafer surface. The method of producing a uniform wear rate on the surface of a polishing article or on the surface of a polishing pad is discussed in U.S. Patent Nos. 5, m, 9G8; ^ 297, 364; 5, 486, 129; 5, 230, 184; 5, 245, 790; ^ 5, 562, 530: These two methods are applicable to the present invention. . It is also possible to replace the strip or roll of the three-dimensional abrasive composite with the work of the present invention, and to use the endless flattening process of the endless belt or the supply roll using the sheet material to combine the polishing slurry, and the monthly work grinding system. The amount applied to the surface of the wafer is preferably sufficient to assist in the removal of the copper or copper oxide layer from the surface. In most cases, there is sufficient slurry from the operation of the present invention. It should also be understood that in the case of the above-described polishing applications, in addition to the slurry of the present invention, the first grinding burn may be required at the flattening interface. This second abrasive poly can be the same as the first abrasive poly, or: different. The flow rate of the grinding operation in the dispersion operation is usually in the range of about kr., and is preferably cc/min, and more preferably about 2.5 to 250 ml/min. The surface finish can be evaluated by known methods. A preferred method is to = "Rt value of the rounded surface" which provides a measure of "thickness" and which exhibits scratches or other surface defects. Preferably, the surface of the wafer is modified to produce no

O:\89\89646DOC -22· 1305668 and even more preferably no greater than about 1000 angstroms, more preferably no greater than about 100 angstroms greater than about 50 angstroms. There are many process steps for single-semiconductor wafers. Therefore, a relatively high metal layer removal material is required. The removal rate of the slurry (10) of the present invention as described herein is generally at least 1 angstrom per minute, preferably at least 2000 angstroms per minute, more preferably at least 3 angstroms per minute, and most preferably At least side angstroms per minute. The rate of metal removal can be seen from the CMP tool and the type of wafer surface to be processed. It is generally desirable to have a high removal rate, which is a loss rate that does not impair the desired surface finish and/or topography of the wafer surface. Process. EXAMPLES The invention is further described in the following non-limiting examples. Example 1 This example demonstrates the effect of an organic polysulfide solution to remove copper from a semiconductor wafer. The copper crystals were round polished using a solution of ethyl polysulfide (HEPS) having a nominal 4·5 sulfur rating. HEPS was dissolved in ethanol. A 11 £1 solution was added to a 1:1 mixture of three parts ethanol and water. Use 3 PSI (or 2 684 晶圆 wafer pressure ' 4 吋 copper wafer to rotate at 8 rpm (or 〇 · 62 m per pad - wafer relative speed). The polishing pad is ruler 4611 (: - 1000 perforated pad. ^1£% slurry flow rate is 80 cc per minute at the center of the pad. Copper removal rate is i 141 nm / min. Example 2 Cut pure copper foil into strips of about 4 cm by 4 cm. In a 60 C solution of gram per liter of sodium hydroxide, the copper was cationically cleaned at 4.0 volts for 3 sec. After cleaning, the copper foil was washed in distilled water and then immersed in 5 〇/〇 sulphuric acid.

〇 \S9\89646 OOC -23- 1305668 seconds. The copper was again washed in distilled water. The copper was immersed in a hydroxyethyl polysulfide (HEPS) solution having a nominal sulfur content of 4.7, pH 7, (50:50 in ethanol) for 30 minutes. The weight changes due to the formation of the polysulfide film are shown in the table below. Minutes initially weight final weight difference weight increase % 5 0.1134 0.1153 0.0019 1.68% 10 0.108 0.1173 0.0093 8.61% 15 0.133 0.15 0.017 12.78% 20 0.149 0.1703 0.0213 14.30% 25 0.1191 0.1426 0.0235 19.73% 30 0.1069 0.1362 0.0293 27.41% Self-polysulfide After the solution was removed, the copper increased in weight and all samples darkened. The increase in the weight after the impregnation is caused by the formation of a copper (II) sulfide coating. Example 3 A sample of the above Example 2 was immersed in distilled water for 5 minutes, and then the copper sulfide was wiped with a thick cotton cloth to remove the polysulfide film. The foil is then weighed again and the copper loss due to worn copper sulfide is shown in the table below: Minutes Initial Weight Final Weight Weight Difference Weight Increase % 5 0.1134 0.1112 -0.0022 -1.94% 10 0.108 0.1021 -0.0059 -5.46% 15 0.133 0.1234 -0.0096 -7.22% 20 0.149 0.1368 -0.0122 "-8.19% 25 0.1191 0.105 -0.0141 -11.84% 30 0.1069 0.0917 -0.0152 -14.22% Example 4 This example shows the effect of pH change in a polysulfide slurry. \89\89646 DOC -24- 1305668 Clean copper foil as discussed. Immerse copper in a hydroxyethyl polyfluorene solution (50··50 in ethanol) with a nominal sulfur content of 4·7, pH 5 3 30 minutes. The weight change due to the formation of polysulfide film is shown in the table below. Minute initial weight final weight difference ^ weight increase % 5 0.0982 0.0986 0.0004 〇-41%~~~ 10 0.1072 0.1107 0.0035 3.26% 15 0.1413 0.1484 0.0071 5.02 % 20 0.122 0.1329 ~~8^93%~~~' 25 0.1355 0.1523 0.0168 12.40% — 30 0.1073 0.1258 -------- 0.0185 ------- 17.24%^ ------ After the removal of the polysulfide solution, the steel increases the weight and all the samples become dark. The subsequent weight increase is due to the formation of a copper sulfide coating. The vulcanized steel layer is removed as discussed in Example 3, and the copper is reweighed. The copper weight loss due to the removal of the broken copper layer is shown below. Table. Weight increase 〇/. Minute initial weight Final weight difference 0.0982 0.1072 0.0979 -0.0003 0.31〇/〇0.1059 -0.0013

30 0.1073 0.1031 0.0042 •3.910/0 Copper loss is low at low pH Example 5 This example shows the effect of cosolvent on copper removal rate. Clean the copper drop as discussed in Example ^ above. A hydroxyethyl polysulfide/liquid mixture (50:50 in ethanol) having a nominal sulfur content of 4.7, pH 7, was diluted with water to a concentration of 1% iHEps. Copper immersion

O:\89\89646.DOC -25 - l3〇5668 Initial weight Final weight Weight difference Weight increase % 0.1424 0.1452 0.0028 1.97% 0.1430 — 1 - 0.1565 0.0135 9.44% 0.1484 J------ 0.1603 0.0119 ” 8.02% Removal The weight loss caused by the copper sulfide layer and the sulfide layer is shown in the following table: __minute initial weight final weight difference 0.1424 0.1416 -0.0008 ' -- L_1_5 _ 0.1430 0.1421 -0.0009 0.1484 0.1469 -0.0015 Example 6 This is another use An example of a mixed organic-aqueous solvent system. The copper foil was cleaned as discussed in Example 1 above. An ethyl polysulfide solution (50:50 in ethanol) having a nominal sulfur content of 4.7, pH 7 was diluted with water to a 25% hEPS concentration. Immerse the copper for 5 to 15 minutes. The weight change due to the formation of the polysulfide film is shown in the table below. Minutes First Weight Final Weight Weight Difference % Weight Increase 1 0.1415 0.1463 0.0048 3.39% 5 — sec 0.1339 0.1365 0.0026 1.94% 15 0.1459 0.1498 0.0039 2.67% The copper sulfide layer was removed as described in Example 2 above and the copper was reweighed. The weight loss of copper caused by copper sulfide layer removal is shown in the following table: Minutes Initial Weight Final Weight Weight Difference Weight Increase % 1 0.1415 0.1404 -0.0011 -0.78% 5 0.1339 0.1306 -0.0033 -2.46% 15 0.1459 0.1399 -0.006 -4.11% O: \89\89646 DOC •26 - 1305668 Example 7 This example shows the use of Juwei in a 70 all-aqueous medium. The copper foil was cleaned as discussed in Example I above. The copper is immersed in sulfur in a polysulfate solution of acetic acid (4% by weight in water, and has a nominal sulfur content of 4' pH 5.3) for 5 to 30 minutes. The weight changes due to the formation of polysulfide are shown in the table below. The copper sulfide was removed and removed as discussed in Example 2 above. Copper loses a high proportion of its original weight due to the formation of a polysulfide layer. 1—minutes initial weight final weight difference weight increase % 5 0.1375 0.0858 -0.0517 -37.60% 10 0.1199 0.0809 -0.039 -32.53% __ 15 0.1408 0.0945 -0.0463 -3 2.88% 20 0.1276 0.0855 -0.0421 -3 2.99% 25 0.1436 0.0873 -0.0563 -39.21% 30 0.1395 0.0734 -0.0661 -47.38% O:\89\89646.DOC -27-

Claims (1)

1305668 Pickup, Patent Application Range: ι_ A slurry that can be used to planarize the surface of a wafer suitable for the fabrication of semiconductor devices. The slurry comprises the following: a) a sulfur-containing compound that converts copper into copper sulfide, b) In the case of liquid carrier, c) oxidant as appropriate, d) optionally accommodating particles, e) optionally chelating agent, f) buffer as appropriate, g) passivating agent as appropriate, h) In the case of surfactants, emulsifiers, viscosity modifiers, wetting agents, lubricants, soaps, etc., 0 depending on the situation, the metal polishing selective termination compound, j) co-solvent as appropriate. 2. The slurry according to the scope of the patent application, wherein the sulfur-containing compound capable of converting copper into copper sulfide is a disulfide or polysulfide RiS-Sx-S-R2 having the following structure: wherein R丨 and r2 are independently It is an organic or inorganic part, and 乂 is an integer of 24 to 。. 2, according to the patent scope of the second aspect of the slurry, wherein R 々 R2 independently · ', the organic part, which may include hydrocarbons or functional groups, such as hydrogen, amine, trans-base, = element, thiol, Affiliation, aryl, aryl, or a combination thereof. It is an inorganic functional group which is independently protected from a base or an alkaline earth metal salt or an ammonium salt or a group thereof, 0^8^89646 D〇c 1305668. 5. The slurry according to item 2 of the patent application, wherein the polysulfide is hydroxyethyl polysulfide. Soil 6. The slurry according to item 1, wherein the sulfur-containing compound which converts copper into copper sulfide has a concentration of from 0.0010% to 1%. 7. According to the grinding scope of the third paragraph of the patent application, wherein the inorganic polishing particles are two k from Si〇2 ai2〇3, Ce〇2, oxidized maloc' calcium sulphate, sulphate, garnet, citrate, and Titanium dioxide. 8. Grinding and burning according to item 1 of the patent application, wherein the pH is 2 to 13. 9. A method of modifying a wafer surface suitable for use in the fabrication of a semiconductor device, comprising the steps of: ~ a) providing a wafer comprising a first material having a surface patterned with a surname and deposited on the first a second material on the surface of the material; b) in the presence of a working slurry containing a sulfur compound capable of converting copper to copper sulfide, bringing the second material of the wafer into contact with the abrasive crucible and c) moving the wafer relatively or polishing The pad simultaneously contacts the second material to the polishing pad until the exposed surface of the wafer is flat and includes at least one exposed first material region and one exposed second material region. The method of claim 9, wherein the abrasive poly-containing polishing particles. 11. The method of claim 9, wherein the polishing particles are fixed to the polishing crucible. 12. The method of claim 9, wherein the polishing crucible comprises grinding water and water D, the grinding 35 comprising a plurality of slack abrasive particles dispersed at 0\89\89646.DOC -2- 1305668 13. 15. 16. 17. Grinding Poly" This slurry contacts the metal layer of the wafer by applying a polishing pad. The method of claim 12, wherein the first material is a dielectric material and the second material is a conductive material. The method of claim 12, wherein the wafer further comprises a barrier layer covering the dielectric material. The method of claim 12, wherein the metal layer is selected from the group consisting of titanium, silver, aluminum, tungsten, tantalum, nitride, tungsten nitride, tantalum oxide, tungsten oxide, tantalum oxide, copper Or its alloy. The method of claim 12, wherein the high impact water is used to remove the worn copper sulfide particles. According to the method of claim 12, the ultrasonic radiation is used to help remove copper sulfide from the surface of the wafer. O:\89\89646 DOC